Process for the preparation of methyl tertio-butyl ether

Abstract: Methyl tertiary butyl ether (MTBE) is formed by reaction of methanol with tertiary butyl alcohol in two catalyst beds. A feedstock mixture comprising methanol and tertiary butyl alcohol in a molar ratio of 2 to 3 moles of methanol per mole of tertiary butyl alcohol is reacted in a first etherification reaction zone at a liquid hourly space velocity of 1 to 10 volumes of feedstock mixture per volume of catalyst per hour. A first reaction product mixture is fractionated to remove MTBE as an overhead fraction. The bottoms fraction comprising unreacted methanol and tertiary butyl alcohol is passed to a second etherification reaction zone at a liquid hourly space velocity of 0.5 to 4. A second reaction product mixture is fractionated to recover additional MTBE.

Description: The invention relates to a process for the manufacture and purification of methyl tertiary butyl ether. More particularly, the invention relates to a process for the reaction of tertiary butyl alcohol with methanol and purification of the methyl tertiary butyl ether containing reaction product mixture formed by the reaction. Concern for environmental pollution and human health disorders caused by lead from exhaust gases of internal combustion engines has motivated a reformulation of automobile gasoline to remove lead containing compounds. In order to make an unleaded gasoline of the same octane number, high octane oxygenated hydrocarbon compounds have been substituted for tetraethyl lead in the automobile gasoline formula. A number of oxygenated hydrocarbon compounds are known to have high octane numbers. In particular, methyl t-butyl ether (MTBE), ethyl t-butyl ether (ETBE), isopropyl t-butyl ether, t-amyl methyl ether (TAME) and t-butyl alcohol (tBA) are used commercially to increase the octane number of automobile gasoline. The preparation of these ethers by the catalytic addition of an alcohol to an olefin having a double bond adjacent to a tertiary carbon atom has been extensively studied. Macroreticular acid resin catalysts are the preferred catalysts for the process. US-A-5243091 teaches a method for preparing methyl tertiary butyl ether from methanol and tertiary butyl alcohol. Isobutylene is used downstream of the etherification reaction zone as an extractant in the purification of methyl tertiary butyl ether. Isobutylene is also reacted with methanol to yield additional methyl tertiary butyl ether. There is a need for a process which provides a high recovery level of MTBE in comparison to the prior art which is simple to perform. In the present invention, tertiary butyl alcohol is reacted with methanol to produce methyl tertiary butyl ether. The reaction is carried out in two catalytic reaction zones. The feedstock comprises a mixture of methanol and tertiary butyl alcohol in a molar ratio of 2 to 3 moles of methanol per mole of tertiary butyl alcohol. All of the feedstock is passed to the first reaction zone at a liquid hourly space velocity of 1 to 10 volumes of feedstock per catalyst volume per hour. The first reaction product mixture is fractionated to yield a first lighter distillate fraction comprising isobutylene, methanol and methyl tertiary butyl ether and a second heavier distillate fraction comprising methanol, tertiary butyl alcohol and water. The second heavier distillate fraction is passed to the second reaction zone at a liquid hourly space velocity of 0.5 to 4 volumes of feedstock per volume of catalyst per hour. The second reaction product mixture is fractionated to yield a third lighter distillate fraction comprising isobutylene, methanol and methyl tertiary butyl ether and a fourth heavier distillate fraction comprising methanol, tertiary butyl alcohol and water. Methyl tertiary butyl ether is recovered from the first and third fractions. The second and fourth fractions are recycled to produce more methyl tertiary butyl ether. It is seen that in accordance with the methyl tertiary butyl ether (MTBE) manufacture and purification method of the present invention, two separate etherification reaction zones, each containing a bed of etherification catalyst, are utilized. A wide variety of etherification catalysts can be used for this purpose, such as supported acid-type catalysts. A preferred catalyst is a sulfonic acid resin etherification catalyst such as a sulfonated polystyrene resin cross-linked with divinyl benzene. Any suitable solid resin etherification catalyst may be used for this purpose, such as a strongly acidic ion exchange resin consisting essentially of sulfonated polystyrene, such as a divinyl benzene cross-link polystyrene matrix containing from 0.5 to 20% of copolymerized divinyl benzene. Resins of this nature are manufactured and sold commercially under various trade names such as Dowex® 50, Dowex® M-31, Nalcite® HCR, Amberlyst® 16 and Amberlyst® 15. The use of this type of catalyst is disclosed, for example, in US-A-4144138. Also, Kieselguhr impregnated with phosphoric acid as disclosed is US-A-2282469, titania having phosphoric acid impregnated thereon as disclosed in US-A-4822921 or a heteropolyacid such as 12-tungstophosphoric acid or 12-molybdophosphoric acid supported on titania, may be used. Zeolites or aluminosilicate zeolites as disclosed in US-A-4058576 may also be used. The reaction conditions to be utilized when reacting methanol with tertiary butyl alcohol in the presence of a sulfonic acid resin etherification catalyst include a reaction temperature of 35°C to 140°C, a pressure of 0.2 to 3.5 MPa (30 to 500 psia) and a space velocity of 0.5 to 20 volumes of feed per volume of etherification catalyst per hour. In accordance with the present invention, a distillate fraction obtained during the recovery process, identified as a second heavier distillation fraction, and which contains both methanol and tertiary butyl alcohol, is brought into contact with a solid resin etherification catalyst in order to convert a significant portion of the methanol and residual tertiary butyl alcohol to methyl tertiary butyl ether. Any suitable solid resin etherification catalyst may be used for this purpose, such as described above. The first distillation fraction will normally contain from 5 wt.% to 15 wt.% of isobutylene, from 70 wt.% to 80 wt.% of methyl tertiary butyl ether and from 10 wt.% to 20 wt.% of methanol. The second distillation fraction will normally contain from 40 wt.% to 60 wt.% of methanol, from 20 wt.% to 40 wt.% of tertiary butyl alcohol, from 15 wt.% to 35 wt.% of water and less than 1 wt.% methyl tertiary butyl ether. The second distillation fraction is contacted with a solid resin etherification catalyst in the second etherification reaction zone under conversion conditions including, for example, a temperature of 35°C to 140°C, a pressure of 0.2 to 3.5 MPa (30 to 500 psia) and a LHSV of 0.5 to 4 volumes of second distillation fraction per volume of etherification catalyst per hour. As a consequence, a second reaction product mixture is formed which will normally contain from 0.5 wt.% to 3.0 wt.% of isobutylene, 15 wt.% to 30 wt.% of methyl tertiary butyl ether, 30 wt.% to 50 wt.% of methanol, and from 5 wt.% to 20 wt.% tertiary butyl alcohol. The flow of methanol and tertiary butyl alcohol feedstock is regulated so that a molar excess of methanol is present in both the first and second etherification reaction zones, for example, a molar ratio of 1.1 moles to 3 moles of methanol per mole of tertiary butyl alcohol. The methanol and tertiary butyl alcohol in the second etherification zone is the unreacted product of the first etherification zone. It is preferred to provide a molar ratio in the first etherification zone of 2 to 3 moles of methanol per mole of tertiary butyl alcohol. This will provide a molar excess of 1.1 to 2 moles of methanol per mole of tertiary butyl alcohol to the second etherification reaction zone without excessive reclaiming of methanol. Within the etherification reaction zones methanol exothermically reacts with the tertiary butyl alcohol to form methyl tertiary butyl ether which is contained in a reaction product discharged from the etherification reaction zone to a methyl tertiary butyl ether (MTBE) distillation zone. As a specific example, when the solid etherification catalyst is a sulfonic acid resin such as Amberlyst® 15 and when the molar ratio of methanol to tertiary butyl alcohol in the feed mixture charged to the first etherification reaction zone is the ratio of 2.0 moles of methanol per mole of tertiary butyl alcohol, and the reaction is conducted at a temperature of 110°C at a liquid hourly space velocity of 2.0 volumes of feed mixture per volume of catalyst per hour, the first etherification reaction product may have the composition in part shown by the following table: Component Wt % Water 14.0 Methanol 27.6 Isobutylene 3.0 tBA 14.1 MTBE 34.5 Other 6.8 The first etherification reaction product charged to the first MTBE distillation zone is fractionated therein under distillation conditions including a liquid reflux temperature of 30°C to 100°C, and more preferably 40°C to 80°C, a reboiler temperature of 80°C to 115°C, and more preferably from 95°C to 105°C, and a pressure of 0.1 to 0.4 MPa (15 psia to 60 psia), the distillation condition being selected such that substantially all of the MTBE in the etherification reaction product is taken overhead from the first distillation zone. As a consequence, the first distillation fraction taken overhead from the distillation zone will comprise substantially all of the isobutylene and substantially all of the methyl tertiary butyl ether and some of the methanol charged to the first distillation zone. The second heavier distillation fraction discharged from the first MTBE distillation zone will comprise methanol, tertiary butyl alcohol and water. Typically, the conversion to MTBE in the second etherification zone will amount to 30 mole% to 70 mole%, based on the tertiary butyl alcohol. A second reaction product mixture is formed. The composition of a typical second reaction product mixture is characterized as follows: Component Wt. % MTBE 19.8 Methanol 40.3 tBA 12.0 Isobutylene 1.1 Water 26.8 The second reaction product mixture is charged to a second MTBE distillation zone and fractionated under distillation conditions including a reboiler temperature of 80°C to 115°C, preferably 95°C to 105°C, and a pressure of 0.1 to 0.4 MPa (15 to 50 psia). Distillation conditions are selected so that substantially all of the MTBE is taken overhead. As a result, a third lighter distillation fraction comprises methyl tertiary butyl ether, isobutylene, unreacted methanol and less than 1 wt.% tertiary butyl alcohol (tBA). A fourth heavier distillation fraction comprises the remaining unreacted methanol, tertiary butyl alcohol and water. The first lighter distillation fraction and third lighter distillation fraction are typically subjected to solvent extraction to remove methanol. Within the methanol solvent extraction zone, solvent extraction conditions are established for countercurrent solvent extraction including a ratio of water to extraction feed mixture within the range of 0.1 to 0.3 parts of water per part of extraction feed mixture per hour, and more preferably a ratio of 0.1 to 0.2 parts of water per part of extraction feed mixture. Extractive conditions to be established may suitably include a temperature of 20°C to 60°C and more preferably from 30°C to 40°C, and a pressure of 0.3 to 3.5 MPa (50 to 500 psia) and more preferably from 0.3 to 1.0 MPa (50 to 150 psia). As a result, a raffinate is formed comprising isobutylene, methyl tertiary butyl ether and a minor amount of water. An extract is formed comprising methanol, water and a minor amount of methyl tertiary butyl ether. In a preferred embodiment, the raffinate is passed to a third methyl tertiary butyl ether distillation zone to produce a fifth lighter distillation fraction comprising isobutylene and water and a sixth heavier distillation fraction consisting essentially of methyl tertiary butyl ether. This invention is shown by way of Example. EXAMPLE 1A Amberlyst® 15 macroreticular, acid resin catalyst was soaked in methanol for 2 days. A 25cc portion of the presoaked catalyst was charged to a first upflow, tubular reactor. Another 25cc portion of the presoaked catalyst was charged to a second upflow tubular reactor. Feedstock comprising methanol and tertiary butyl alcohol was charged to the first reactor in a molar ratio of 2 to 3 moles of methanol per mole of tertiary butyl alcohol. The first reactor product was fractionated to recover essentially all methyl tertiary butyl ether overhead. The fractionation bottoms was passed to the second reactor. The tertiary butyl alcohol conversion was 60.4%. The selectivity of the conversion of tertiary butyl alcohol to methyl tertiary butyl ether was 91.9%. The following data was recorded: REACTION CONDITIONS Stream Temperature LHSV Pressure Time on First 110°C 4 to 10 2.17 MPa 28 hours Second 110°C 2 2.17 MPa 28 hours FEED COMPOSITION TO SECOND REACTOR Water 22.5 wt% Methanol 47.5 wt% t-butyl alcohol 28.4 wt% di-tertiary butyl peroxide 0.9 wt% methyl tertiary butyl ether 0.7 wt% EXAMPLE 1B Amberlyst® 16 macroreticular, acid resin catalyst was soaked in methanol for 2 days. A 25cc portion of the presoaked catalyst was charged to a first upflow, tubular reactor. Another 25cc portion of the presoaked catalyst was charged to a second upflow tubular reactor. Feedstock comprising tertiary butyl alcohol and methanol in a molar ratio of 2 to 3 moles of methanol per mole of tertiary butyl alcohol was charged to the first reactor. The first reactor product was fractionated to recover all methyl tertiary butyl ether overhead. The fractionation bottoms was passed to the second reactor. A second reactor product was recovered. The tertiary butyl alcohol conversion was 59.1%. Selectivity of the tertiary butyl alcohol conversion to methyl tertiary butyl ether was 91.2%. The following data was recorded. REACTION CONDITIONS Stream Temperature LHSV Pressure Time on First 110°C 4 to 10 2.17 MPa (314.7 psia) 472 hours Second 110°C 2 2.17 MPa (314.7 psia) 472 hours FEED COMPOSITION TO SECOND REACTOR Water 22.5 wt% Methanol 47.2 wt% t-butyl alcohol 28.4 wt% di-tertiary butyl peroxide 0.9 wt% methyl tertiary butyl ether 0.7 wt% Other 0.3 wt%

Claims: A process for reacting tertiary butyl alcohol with methanol to produce methyl tertiary butyl ether comprising the steps of: a) passing a feed mixture comprising methanol and tertiary butyl alcohol in a molar ratio of 2 to 3 moles of methanol per mole of tertiary butyl alcohol through a first etherification reaction zone containing etherification catalyst under etherification conditions at a liquid hourly space velocity of 1 to 10 volumes feed mixture per catalyst volume per hour to form a first reaction product mixture; b) passing the first reaction product mixture to a first distillation zone and separating into a first lighter distillate fraction comprising isobutylene, methanol and methyl tertiary butyl ether and a second heavier distillate fraction comprising methanol, tertiary butyl alcohol and water; c) passing the second heavier distillate fraction to a second etherification reaction zone containing etherification catalyst under etherification conditions at a liquid hourly space velocity of about 0.5 to 4 volumes feed mixture per catalyst volume per hour to form a second reaction product mixture; d) passing the second reaction product mixture to a second distillation zone and separating into a third lighter distillate fraction comprising isobutylene, unreacted methanol and methyl tertiary butyl ether and a fourth heavier distillate fraction comprising unreacted methanol, tertiary butyl alcohol and water. A process as claimed in Claim 1 additionally comprising: e) passing the third lighter distillate fraction to a methanol extraction zone and countercurrently contacting the third lighter distillate fraction with water to produce a raffinate comprising isobutylene, methyl tertiary butyl ether and a minor amount of water and an extract comprising methanol, water and a minor amount of methyl tertiary butyl ether. f) passing the raffinate to a third methyl tertiary butyl ether distillation zone and separating it therein into a fifth lighter distillation fraction comprising isobutylene and water and a sixth heavier distillation fraction consisting essentially of methyl tertiary butyl ether. A process as claimed in Claim 1 or Claim 2, wherein the second heavier distillation fraction comprises less than 1 wt.% methyl tertiary butyl ether. A process as claimed in Claim 1 or Claim 2, wherein the fourth heavier distillation fraction comprises less than 1 wt.% methyl tertiary butyl ether.

Inventors: BENAC BRIAN LAWRENCE, KRUSE CHARLES JOSEPH, PRESTON KYLE LEE, BENAC, BRIAN LAWRENCE, KRUSE, CHARLES JOSEPH, PRESTON, KYLE LEE
Applicants: HUNTSMAN SPEC CHEM CORP, HUNTSMAN SPECIALTY CHEMICALS CORPORATION
Application year: 1994
Main classification: C07C41
IPC codes: B01J31, C07C41, C07B61, C07C43